JP2010525551A - Electrochemical cell and energy storage device with non-graphitizable carbon electrode - Google Patents

Electrochemical cell and energy storage device with non-graphitizable carbon electrode Download PDF

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JP2010525551A
JP2010525551A JP2010507817A JP2010507817A JP2010525551A JP 2010525551 A JP2010525551 A JP 2010525551A JP 2010507817 A JP2010507817 A JP 2010507817A JP 2010507817 A JP2010507817 A JP 2010507817A JP 2010525551 A JP2010525551 A JP 2010525551A
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energy storage
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anode
electrochemical cell
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ペーテル ビルケ，
ミヒアエル ケレル，
一博 高橋
英男 矢部
聖子 阿部
和典 小澤
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Enax Inc
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Abstract

本発明は、隔離体により隔離される陰極（Ｋ）及び陽極（Ａ）を持つ電気化学単電池（２）に関し、陰極（Ｋ）が少なくともリチウム遷移金属酸化物に基く活物質を含み、陽極（Ａ）が少なくとも０．７Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を陽極（Ａ）が含んでいる。
【選択図】図２The present invention relates to an electrochemical cell (2) having a cathode (K) and an anode (A) separated by a separator, the cathode (K) comprising an active material based on at least a lithium transition metal oxide, The anode (A) contains a material such that A) has an open circuit voltage curve with a full stroke of at least 0.7V and a steep voltage discharge curve without saddle points.
[Selection] Figure 2

Description

優先権主張Priority claim

本願は、２００７年４月２４日に出願されたドイツ連邦共和国特許出願第１０２００７０１９６２５．５号及び２００７年５月１０日に出願された第１０２００７０２２４３５．６号の優先権を主張するものであり、これらの出願の内容はこの出願に加入されている。  This application claims the priority of German Patent Application No. 102007019625.5 filed on Apr. 24, 2007 and No. 102007022435.6 filed on May 10, 2007. The contents of this application are incorporated in this application.

本発明は、電気化学単電池及び複数のこのような電気化学単電池を含むエネルギー貯蔵装置及びこれを使用する電気自動車又はハイブリッド電気自動車に関する。エネルギー貯蔵装置（いわゆる電池パック）は複数の平らな電気化学単電池（電池単電池とも称される）を含み、各単電池は例えば外部端子を介して電気化学単電池を互いに電気的に接続する１対の電極を含んでいる。  The present invention relates to an electrochemical cell, an energy storage device comprising a plurality of such electrochemical cells, and an electric vehicle or hybrid electric vehicle using the same. An energy storage device (so-called battery pack) includes a plurality of flat electrochemical cells (also referred to as cell cells), and each cell electrically connects the electrochemical cells to each other, for example, via an external terminal. A pair of electrodes is included.

応用例えば電気自動車、ハイブリッド自動車、電気工具等のために高い入−出力電力源のような要求を満たすために、新しいエネルギー貯蔵装置例えば鉛蓄電池、ニッケル金属ハイブリッド電池、ニッケル−カドミウム電池及び電気二重層コンデンサ等が開発されている。  New energy storage devices such as lead acid batteries, nickel metal hybrid batteries, nickel-cadmium batteries and electric double layers to meet demands such as high input-output power sources for applications such as electric vehicles, hybrid vehicles, electric tools etc. Capacitors have been developed.

これらの新しいエネルギー貯蔵装置は、駆動電動機及び車載電気システムに電力を供給する。エネルギー貯蔵装置の充−放電過程を制御するため、充−放電過程、制動エネルギーから電気エネルギーへの変換（回生制動）等を管理する制御器が統合されているので、エネルギー貯蔵装置は自動車の作動中に充電することができる。  These new energy storage devices provide power to drive motors and onboard electrical systems. In order to control the charge-discharge process of the energy storage device, the controller that manages the charge-discharge process, conversion from braking energy to electrical energy (regenerative braking), etc. is integrated, so the energy storage device operates the vehicle Can be charged inside.

エネルギー貯蔵装置又は各電気化学単電池は、４００Ａの電流で、極端な条件例えば高い温度に対して５００Ａまでの電流で、１００Ｖ〜４５０Ｖの最大電圧範囲のような良い特性を示さねばならない。連続的な電流は８０Ａ〜１００Ａ又は応用に応じてもっと大きい範囲にある。  The energy storage device or each electrochemical cell must exhibit good characteristics, such as a maximum voltage range of 100V to 450V under extreme conditions, such as up to 500A for extreme conditions, for example at a current of 400A. The continuous current is in the range of 80A-100A or more depending on the application.

このように極端な条件のために、エネルギー貯蔵装置の電気化学単電池の接続部は極端に応力を受ける。  Due to such extreme conditions, the connection of the electrochemical cell of the energy storage device is extremely stressed.

従って本発明の目的は、例えば電気自動車又はハイブリッド電気自動車において、極端な充−放電条件下で、例えば１５年まで高い作動安全性及び高い信頼性を持つ電気化学単電池及びエネルギー貯蔵装置を提供することである。  Accordingly, an object of the present invention is to provide an electrochemical cell and energy storage device with high operational safety and high reliability, for example up to 15 years, under extreme charge-discharge conditions, for example in an electric vehicle or a hybrid electric vehicle. That is.

この目的を達するため、電気化学単電池が、再充電可能な電池特に再充電可能なリチウムイオン電池又は陰極及び陽極のための電極材料の新規な組合わせを備えている。  To achieve this objective, electrochemical cells are equipped with a new combination of electrode materials for rechargeable batteries, in particular rechargeable lithium ion batteries or cathodes and anodes.

本発明の重要な局面によれば、電気化学単電池が、隔離体により隔離される陰極及び陽極を持ち、陰極が少なくともリチウム遷移金属酸化物に基く二相活物質を含み、陽極が少なくとも０．７Ｖ特に１．３Ｖ以上例えば１．５Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を陽極が含んでいる。この材料は、少なくとも黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料である。その代りに、この材料は、二酸化タングステン又は他の適当な接合金属酸化物又は金属リチウムである。  According to an important aspect of the present invention, an electrochemical cell has a cathode and an anode separated by a separator, the cathode comprising a two-phase active material based on at least a lithium transition metal oxide, and the anode is at least 0. 0. The anode contains a material having an open circuit voltage curve with a total stroke of 7V, especially 1.3V or more, for example 1.5V, and a steep voltage discharge curve without saddle points. This material is a non-graphitizable carbon material that has at least a higher lattice disorder than graphite. Instead, the material is tungsten dioxide or other suitable bonding metal oxide or metal lithium.

陰極は、なるべく少なくとも活物質、特にリチウム遷移金属酸化物例えばリチウムマンガンスピネル（ＬｉＭｎ２Ｏ４）、燐酸鉄リチウム（ＬｅＦｅＰＯ４）、燐酸コバルトリチウム（ＬｉＣｏＰＯ４）、又は燐酸マンガンリチウム（ＬｉＭｎＰＯ４）、又はＬｉ（Ｃｏ１／３Ｎｉ１／３Ｍｎ１／３）Ｏ２又はＬｉ（Ｎｉ１．５Ｍｎ０．５）Ｏ２，ＬｉＣｏＯ２，Ｌｉ（Ｎｉ０．８Ｃｏ０．２）Ｏ２（部分的にＡｌを付与される）のような他の適当な燐酸塩に基く二相活物質を含んでいる。The cathode is preferably at least an active material, in particular a lithium transition metal oxide such as lithium manganese spinel (LiMn 2 O 4 ), lithium iron phosphate (LeFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), or lithium manganese phosphate (LiMnPO 4 ), Or Li (Co 1/3 Ni 1/3 Mn 1/3 ) O 2 or Li (Ni 1.5 Mn 0.5 ) O 2 , LiCoO 2 , Li (Ni 0.8 Co 0.2 ) O 2 ( Including other suitable phosphate-based biphasic active materials (partially Al).

陰極材料としてのリチウム遷移金属酸化物と、陽極材料としての黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料とのこのような材料組合わせは、高い単電池安全性と高い費用効率を持つ高い信頼性を可能にする。更に単電池は、単電池質量又は単電池体積の増大なしに高い充−放電能力に基く高寿命の期待を持っている。この電極材料組合わせに基くこのような電気化学単電池は、簡単かつ効率的かつ非常に速やかに製造可能である。単電池特に電極活物質を持つ膜表面は、単電池の高いエネルギー密度のために効果的に最適化される。  Such a material combination of a lithium transition metal oxide as the cathode material and a non-graphitizable carbon material with a higher lattice disorder than graphite as the anode material is highly cell safe and cost effective. Enables high reliability with. In addition, cells have a long life expectancy based on high charge-discharge capability without increasing cell mass or cell volume. Such an electrochemical cell based on this electrode material combination can be manufactured simply, efficiently and very quickly. The cell surface, particularly the membrane surface with the electrode active material, is effectively optimized for the high energy density of the cell.

陰極材料としてのリチウム遷移金属酸化物の使用は、リチウムとの可逆的な反応を可能にする。これは、リチウムが添加される時格子構造が実質的に変化しないような内位添加形反応を必要とする。更に挿入及び除去の際リチウムとの非常に速い反応が行われるので、高い電力密度が得られる。更にリチウム遷移金属酸化物は普通の低価格の材料である。  The use of a lithium transition metal oxide as the cathode material allows a reversible reaction with lithium. This requires an internal addition type reaction in which the lattice structure does not change substantially when lithium is added. Furthermore, a very fast reaction with lithium takes place during insertion and removal, so that a high power density is obtained. In addition, lithium transition metal oxides are common low cost materials.

陽極用の黒鉛化不可能な炭素材料が非晶質炭素を含む硬質炭素又は軟質炭素であるのがよい。このような陽極用の硬質炭素又は軟質炭素と陰極用リチウム遷移金属酸化物の電極材料組合わせは、電圧／充電状態曲線（Ｖ／ＳｏＣ）特に急な増大を持つ電圧放電曲線を示すので、単電池回復の場合陽極におけるリチウムめっきの危険が回避される。同時に電圧／充電状態曲線の急な増大は、充電状態に応じたエネルギー密度及び利用可能な電池容量が強く減少されないような急な増大を示してはならない。  The non-graphitizable carbon material for the anode may be hard carbon or soft carbon including amorphous carbon. Such an electrode material combination of hard carbon or soft carbon for the anode and lithium transition metal oxide for the cathode exhibits a voltage / charge state curve (V / SoC), particularly a voltage discharge curve with a sharp increase. In the case of battery recovery, the danger of lithium plating at the anode is avoided. At the same time, the sudden increase in the voltage / charge state curve should not show such a sudden increase that the energy density and available battery capacity as a function of the charge state are not strongly reduced.

可能な実施形態では、硬質又は軟質炭素が、例えば熱分解により分解された炭素繊維例えば綿布である。可能なやり方では、硬質炭素が、リチウム化合物を炭素先駆物質と混合して、陽極の電極導電材料として使用される硬質炭素／リチウム化合物混合物を形成することによって、調整される。硬質炭素先駆物質又は軟質炭素先駆物質が、次の成分即ち石油に基くピッチ、フェノール、セルロース、綿布、フェノール樹脂の少なくとも１つ又はその組合わせを含んでいてもよい。このような材料は過放電及び過充電により非常に安定であり、即ち組織を変えないか退化させない。更にこの材料は普通の低価格の材料である。軟質炭素は通常熱硬化性樹脂から成り。軟質炭素は通常熱可塑性樹脂又はピッチから成っている。  In a possible embodiment, the hard or soft carbon is, for example, carbon fibers that have been decomposed by pyrolysis, such as cotton cloth. In a possible manner, the hard carbon is conditioned by mixing the lithium compound with a carbon precursor to form a hard carbon / lithium compound mixture that is used as the anode electrode conductive material. The hard carbon precursor or soft carbon precursor may comprise at least one or a combination of the following components: petroleum-based pitch, phenol, cellulose, cotton cloth, phenolic resin. Such materials are very stable due to overdischarge and overcharge, i.e. do not change or degenerate the tissue. Furthermore, this material is an ordinary low cost material. Soft carbon usually consists of thermosetting resin. Soft carbon usually consists of a thermoplastic resin or pitch.

本発明の別の実施形態では、電解質隔離体がポリマ又はポリマ複合体を含んでいる。  In another embodiment of the invention, the electrolyte separator comprises a polymer or polymer complex.

本発明の重要な局面によれば、エネルギー貯蔵装置が、複数の平らな電気化学単電池を含み、各単電池が隔離体によって隔離される陰極及び陽極を含み、陰極が、少なくともリチウム遷移金属酸化物を含む金属酸化物に基く二相活物質を含み、陽極が少なくとも０．７Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を陽極が含んでいる。陽極材料が、少なくとも黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料であるのがよい。  According to an important aspect of the present invention, the energy storage device comprises a plurality of flat electrochemical cells, each cell comprising a cathode and an anode separated by a separator, the cathode being at least a lithium transition metal oxide The anode contains a material that includes a two-phase active material based on a metal oxide containing a material, the anode having an open circuit voltage curve having a total stroke of at least 0.7 V and a steep voltage discharge curve without saddle points. It is out. The anode material should be a non-graphitizable carbon material having a lattice disorder higher than at least graphite.

応用に応じて、エネルギー貯蔵装置の電気化学単電池が直列、並列又は直並列接続されている。  Depending on the application, the electrochemical cells of the energy storage device are connected in series, in parallel or in series-parallel.

本発明は、電気自動車、ハイブリッド電気自動車特に並列ハイブリッド電気自動車、直列ハイブリッド電気自動車又は直並列ハイブリッド電気自動車において使用可能である。更に本発明は、風力エネルギーまたは他の発生されるエネルギーを貯蔵するためにも使用可能である。更にエネルギー貯蔵装置は、一次又は二次エネルギー貯蔵装置として、別個に又は他のエネルギー貯蔵装置と組合わせて、車両電力供給システムにおいても使用可能である。  The present invention can be used in an electric vehicle, a hybrid electric vehicle, particularly a parallel hybrid electric vehicle, a series hybrid electric vehicle, or a series-parallel hybrid electric vehicle. Furthermore, the invention can be used to store wind energy or other generated energy. Furthermore, the energy storage device can be used in a vehicle power supply system as a primary or secondary energy storage device, either separately or in combination with other energy storage devices.

本発明が、図面に示す以下の実施例を特に参照して更に説明される。しかしこれらの実施例が革新的な教示の多くの有利な使用の例にすぎないことを理解すべきである。  The invention will be further described with particular reference to the following examples shown in the drawings. However, it should be understood that these embodiments are merely examples of the many advantageous uses of the innovative teachings.

各単電池の外部端子対を介して互いに接続される複数の電気化学単電池を持つエネルギー貯蔵装置を示す。  1 shows an energy storage device having a plurality of electrochemical cells connected to each other via an external terminal pair of each cell. 電気化学単電池を示す。  An electrochemical cell is shown.

本発明は、電気化学単電池及び複数のこれらの単電池を含むエネルギー貯蔵装置に関する。本発明は、種々の応用のために、例えばハイブリッド電気自動車において使用可能であり、ハイブリッド電気自動車は駆動電動機及び内燃機関を持ち、駆動電動機はエネルギー貯蔵装置から供給される電力により駆動される。その代りに、エネルギー貯蔵装置は、エネルギー貯蔵装置から供給される電力により駆動される駆動電動機を持つ電気自動車においても使用可能である。更にエネルギー供給装置は、風又は太陽のエネルギーを貯蔵するために使用可能であり、そのため装置は風又は太陽エネルギープラントに統合されている。  The present invention relates to an electrochemical cell and an energy storage device comprising a plurality of these cells. The present invention can be used for various applications, for example, in a hybrid electric vehicle, which has a drive motor and an internal combustion engine, and the drive motor is driven by electric power supplied from an energy storage device. Instead, the energy storage device can also be used in an electric vehicle having a drive motor driven by electric power supplied from the energy storage device. Furthermore, the energy supply device can be used to store wind or solar energy, so that the device is integrated into a wind or solar energy plant.

図１は、複数の平らな電気化学単電池２（電池単電池又は単一単電池又は角柱単電池とも称される）を持つエネルギー貯蔵装置１（電池パックとも称される）を示す。  FIG. 1 shows an energy storage device 1 (also referred to as a battery pack) having a plurality of flat electrochemical cells 2 (also referred to as battery cells or single cells or prismatic cells).

各電気化学単電池２は１対の電極Ａ及びＫを持ち、１つの電極Ｋが陰極又は正の電極であり、他の電極Ａが陽極又は負の電極である。  Each electrochemical cell 2 has a pair of electrodes A and K. One electrode K is a cathode or a positive electrode, and the other electrode A is an anode or a negative electrode.

各電気化学単電池２は、例えば電極Ａ及びＫとして複数の内部電極膜（図示せず）を含む単電池であり、異なる電極膜が図示しない隔離膜により隔離されている。この隔離膜は例えば非水電解質でゆすぐ。電極用膜の代わりに隔離板も使用可能である。  Each electrochemical cell 2 is, for example, a cell including a plurality of internal electrode films (not shown) as electrodes A and K, and different electrode films are isolated by an isolation film (not shown). The separator is rinsed with, for example, a non-aqueous electrolyte. A separator can also be used in place of the electrode membrane.

電気化学単電池２を互いに電気接続するため、各単電池２の電極Ａ及びＫが外部端子３．Ａ及び３．Ｋに接続されている。応用に応じて、電気化学単電池２は、外部端子３．Ａ及び３．Ｋを介して直列、並列又は直並列に接続可能である。  In order to electrically connect the electrochemical cells 2 to each other, the electrodes A and K of each cell 2 are connected to the external terminals 3. A and 3. Connected to K. Depending on the application, the electrochemical cell 2 may have external terminals 3. A and 3. It can be connected in series, parallel, or series-parallel through K.

図１による実施例は、直列接続される電気化学単電池２を示している。  The embodiment according to FIG. 1 shows an electrochemical cell 2 connected in series.

更に各単電池２はケーシング４により包囲されている。ケーシング４は、１つの単電池２を隣接する単電池に対して絶縁する膜ケーシング又は板ケーシングとして設けることができる。  Further, each unit cell 2 is surrounded by a casing 4. The casing 4 can be provided as a film casing or a plate casing that insulates one unit cell 2 from an adjacent unit cell.

単電池２は、ケーシング４を介して少なくとも電気的に互いに絶縁されているのがよい。更に単電池２は、使用される材料に応じて互いに熱的に絶縁可能である。その代りに単電池２は、ケーシング表面を介して電気的に接続可能である。他の実施例では、材料例えば樹脂が電気絶縁のため単電池２の間に満たされる。  The unit cells 2 may be at least electrically insulated from each other via the casing 4. Furthermore, the unit cells 2 can be thermally insulated from each other depending on the material used. Instead, the unit cell 2 can be electrically connected via the casing surface. In another embodiment, a material such as resin is filled between the cells 2 for electrical insulation.

エネルギー貯蔵装置１全体を、図示しないケーシング例えば板ケーシング又は膜ケーシング（ソフトパックとも称される）により包囲することもできる。  The entire energy storage device 1 can be surrounded by a casing (not shown) such as a plate casing or a membrane casing (also referred to as a soft pack).

エネルギー貯蔵装置１の電気化学単電池２の１つが、図２に詳細に示されている。  One of the electrochemical cells 2 of the energy storage device 1 is shown in detail in FIG.

電気化学単電池２はリチウムイオン電気化学単電池である。  The electrochemical cell 2 is a lithium ion electrochemical cell.

本発明の可能な実施例において、各電気化学単電池２は、隔離体Ｅにより隔離される陽極Ａ及び陰極Ｋを含んでいる。電気化学単電池２を他の単電池と電気接続するため、電極Ａ，Ｋが導体５．Ａ，５．Ｋと電気接続されている。これらの“内部”導体５．Ａ，５．Ｋは外部端子３．Ａ，３．Ｋと接続されている。  In a possible embodiment of the invention, each electrochemical cell 2 includes an anode A and a cathode K that are separated by a separator E. In order to electrically connect the electrochemical cell 2 to other cells, the electrodes A and K are conductors 5. A, 5. K is electrically connected. 4. These “inner” conductors A, 5. K is an external terminal 3. A, 3. K is connected.

陰極Ｋ又は正極は、少なくとも活物質、特にリチウム遷移金属酸化物例えばリチウムマンガンスピネル（ＬｉＭｎ２Ｏ４）、燐酸鉄リチウム（ＬｅＦｅＰＯ４）、燐酸コバルトリチウム（ＬｉＣｏＰＯ４）、又は燐酸マンガンリチウム（ＬｉＭｎＰＯ４）、又はＬｉ（Ｃｏ１／３Ｎｉ１／３Ｍｎ１／３）Ｏ２又はＬｉ（Ｎｉ１．５Ｍｎ０．５）Ｏ２，ＬｉＣｏＯ２，Ｌｉ（Ｎｉ０．８Ｃｏ０．２）Ｏ２（部分的にＡｌを付与される）のような他の適当な燐酸塩に基く二相活物質を含んでいる。陽極又は負極は、陽極Ａが少なくとも０．７Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を含んでいる。陽極材料は、少なくとも黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料であってもよい。The cathode K or the positive electrode is at least an active material, in particular lithium transition metal oxide such as lithium manganese spinel (LiMn 2 O 4 ), lithium iron phosphate (LeFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), or lithium manganese phosphate (LiMnPO 4). ), Or Li (Co 1/3 Ni 1/3 Mn 1/3 ) O 2 or Li (Ni 1.5 Mn 0.5 ) O 2 , LiCoO 2 , Li (Ni 0.8 Co 0.2 ) O 2 containing other suitable phosphate-based biphasic active materials such as (partially given Al). The anode or anode includes a material such that anode A has an open circuit voltage curve with a full stroke of at least 0.7V and a steep voltage discharge curve without saddle points. The anode material may be a non-graphitizable carbon material having a lattice irregularity that is at least higher than that of graphite.

黒鉛化不可能な炭素材料が非晶質炭素を含む硬質炭素又は軟質炭素であるのがよい。硬質又は軟質炭素が、例えば熱分解により分解された炭素繊維例えば綿布であるのがよい。  The non-graphitizable carbon material may be hard carbon or soft carbon including amorphous carbon. The hard or soft carbon may be, for example, carbon fiber decomposed by pyrolysis, such as cotton cloth.

陰極材料としてのリチウム遷移金属酸化物と、陽極材料としての硬質又は軟質炭素とのこのような電極材料組合わせは、少なくとも高エネルギー貯蔵のための台地部なしの最適化された開路電圧曲線、長寿命及び最低価格を得るための最適な組合わせである。更にこのような組合わせの結果として、電池状態の決定が改善される。  Such an electrode material combination of lithium transition metal oxide as the cathode material and hard or soft carbon as the anode material is an optimized open circuit voltage curve, long without plateau for high energy storage, long The best combination to get lifetime and lowest price. Furthermore, as a result of such a combination, the determination of the battery state is improved.

１ エネルギー貯蔵装置
２ 電気化学単電池
３．Ａ 陰極の外部端子
３．Ｋ 陽極の外部端子
４ ケーシング
５．Ａ 内部陰極導体
５．Ｂ 内部陽極導体
Ａ 陽極
Ｋ 陰極1 Energy storage device 2 Electrochemical cell A. External terminal of cathode K External terminal of anode 4 Casing 5 A. Internal cathode conductor B Internal anode conductor A Anode K Cathode

Claims (17)

隔離体により隔離される陰極（Ｋ）及び陽極（Ａ）を持つ電気化学単電池（２）において、陰極（Ｋ）が少なくともリチウム遷移金属酸化物に基く活物質を含み、陽極（Ａ）が少なくとも０．７Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を陽極（Ａ）が含んでいる、電気化学単電池。  In the electrochemical cell (2) having a cathode (K) and an anode (A) separated by a separator, the cathode (K) contains an active material based on at least a lithium transition metal oxide, and the anode (A) is at least An electrochemical cell in which the anode (A) contains a material that has an open circuit voltage curve with a full stroke of 0.7V and a steep voltage discharge curve without saddle points. 陽極（Ａ）が、黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料を含んでいる、請求項１に記載の電気化学単電池。  The electrochemical cell according to claim 1, wherein the anode (A) comprises a non-graphitizable carbon material having a higher lattice disorder than graphite. 黒鉛化不可能な炭素材料が非晶質炭素を含む硬質炭素又は軟質炭素である、請求項１に記載の電気化学単電池。  The electrochemical cell according to claim 1, wherein the non-graphitizable carbon material is hard carbon or soft carbon containing amorphous carbon. 硬質炭素が、例えば熱分解により分解された炭素繊維例えば綿布である、請求項３に記載の電気化学単電池。  The electrochemical cell according to claim 3, wherein the hard carbon is, for example, carbon fiber decomposed by pyrolysis, such as cotton cloth. 硬質炭素が、リチウム化合物を炭素先駆物質と混合して、陽極（Ａ）の電極導電材料として使用される硬質炭素／リチウム化合物混合物を形成することによって、調整される、請求項３に記載の電気化学単電池。  Electricity according to claim 3, wherein the hard carbon is conditioned by mixing a lithium compound with a carbon precursor to form a hard carbon / lithium compound mixture used as the electrode conductive material of the anode (A). Chemical cell. 炭素先駆物質例えば硬質炭素先駆物質又は軟質炭素先駆物質が、次の成分即ち石油に基くピッチ、フェノール、セルロース、綿布、フェノール樹脂の少なくとも１つ又はその組合わせを含んでいる、請求項４に記載の電気化学単電池。  5. A carbon precursor, such as a hard carbon precursor or a soft carbon precursor, comprising at least one of the following components: petroleum-based pitch, phenol, cellulose, cotton cloth, phenolic resin, or combinations thereof. Electrochemical cell. 陰極（Ｋ）が少なくとも燐酸鉄リチウム（ＬｉＦｅＰＯ４）、燐酸コバルトリチウム（ＬｉＣｏＰＯ４）、燐酸マンガンリチウム又は他の適当な燐酸塩を含んでいる、請求項１に記載の電気化学単電池。Cathodes (K) of at least lithium iron phosphate (LiFePO 4), phosphate lithium cobalt (LiCoPO 4), contains the manganese phosphate lithium or other suitable phosphate, electrochemical cells according to claim 1. 隔離体がポリマ又はポリマ複合体を含んでいる請求項１に記載の電気化学単電池。  The electrochemical cell according to claim 1, wherein the separator includes a polymer or a polymer complex. 複数の平らな電気化学単電池（２）を持つエネルギー貯蔵装置（１）であって、各単電池が隔離体によって隔離される陰極（Ｋ）及び陽極（Ａ）を含み、陰極（Ｋ）が、リチウム遷移金属酸化物基く二相活物質を含み、陽極（Ａ）が少なくとも０．７Ｖの全行程を持つ開路電圧曲線及び鞍点なしの急勾配の電圧放電曲線を持っているような材料を陽極（Ａ）が含んでいる、エネルギー貯蔵装置。  An energy storage device (1) having a plurality of flat electrochemical cells (2), each cell comprising a cathode (K) and an anode (A) separated by a separator, wherein the cathode (K) A material comprising a two-phase active material based on a lithium transition metal oxide, wherein the anode (A) has an open circuit voltage curve with a total stroke of at least 0.7 V and a steep voltage discharge curve without saddle points. The energy storage device which (A) contains. 陽極（Ａ）が、少なくとも黒鉛より高い格子不規則性を持つ黒鉛化不可能な炭素材料を含んでいる、請求項９に記載のエネルギー貯蔵装置。  The energy storage device according to claim 9, wherein the anode (A) comprises a non-graphitizable carbon material having a lattice disorder higher than that of graphite. 各単電池（２）が、電気化学単電池（２）を互いに電気的に接続する１対の電極（Ａ，Ｋ）を持っている、請求項９に記載のエネルギー貯蔵装置。  10. Energy storage device according to claim 9, wherein each unit cell (2) has a pair of electrodes (A, K) that electrically connect the electrochemical unit cells (2) to each other. 電気化学単電池（２）が直列接続されている、請求項９に記載のエネルギー貯蔵装置。  The energy storage device according to claim 9, wherein the electrochemical cells (2) are connected in series. 電気化学単電池（２）が並列接続されている、請求項９に記載のエネルギー貯蔵装置。  The energy storage device according to claim 9, wherein the electrochemical cells (2) are connected in parallel. 電気化学単電池（２）が直並列接続されている、請求項９に記載のエネルギー貯蔵装置。  The energy storage device according to claim 9, wherein the electrochemical cells (2) are connected in series and parallel. 請求項９に記載のエネルギー貯蔵装置（１）から供給される電力により駆動される駆動電動機を持つ電気自動車。  An electric vehicle having a drive motor driven by electric power supplied from the energy storage device (1) according to claim 9. 駆動電動機及び内燃機関を持つハイブリッド電気自動車であって、駆動電動機が請求項９に記載のエネルギー貯蔵装置（１）から供給される電力により駆動される、ハイブリッド電気自動車。  A hybrid electric vehicle having a drive motor and an internal combustion engine, wherein the drive motor is driven by electric power supplied from the energy storage device (1) according to claim 9. 自動車電力供給システムにおいて、一次又は二次エネルギー供給装置として別々に、又は互いに組合わされるエネルギー供給装置として、請求項９に記載のエネルギー貯蔵装置の使用。  10. Use of an energy storage device according to claim 9 as an energy supply device separately or combined with each other as primary or secondary energy supply device in a motor vehicle power supply system.
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